Cobalt containing azo dyestuffs



2,871,233 COBALT CONTAINING AZO DYESTUFFS Helmut Pfitzner and OttoKaufmann, Ludwigshafen (Rhine), Germany, assignors to Badische Anilin- &Soda-Fabrik .Aktiengesellschaft, Ludwigshafen (Rhine), Germany NoDrawing.. Application June 14, 1955 Serial No. 515,554

Claims priority, application Germany June 16, 1954 1 Claim. (Cl.260-151) This invention relates to a new group of cobalt containing azodyestufifs having a brown, red or blue color,

and to a method of manufacturing these dyestuifs.

Among the principal objects of this invention are provisions for new azodyestufis which contain in their molecule about one atom of cobalt fortwo organic radicals, each of these radicals having one azo group.

Another object is to provide a method of manufacturing such dyestuffs byreacting particular azo dyestuffs with cobalt compounds.

A further object is to supply new azo dyestuffs having a very good lightfastness which dye wool evenly and which are also suitable for dyeingpolyamide articles such as polyamide fibers and fabrics.

Other objects and advantages will be apparent from the more detaileddescription of the invention.

These objects are accomplished by diazotizing' alkoxy aminobenzenesulfonic acid amides of the general formula wherein X is a hydrogen,halogen, alkyl or alkoxy radical; Y is a hydrogen, alkyl or arylradical; Z is a hydrogen, alkyl or aryl radical; and Alk is an alkylradical.

The diazonium compound is coupled with a phenolic or1-methoxy-2-aminobenzene-5-sulfonamide;1-ethoxy-2-aminob'enzene-4-chloro-5-sulfonamide; l methoxy 2aminobenZene-4-ethoxy-5-sulfonic methylarnide;1-methoxy-2-aminobenzene-4-methoxy-5-sulfonic acid dimethylamide;l-methoxy-2-aminobenzene-4-chloro-S-sulfonic acid dimethylamide; 1methoxy 2 aminobenzene 4 chloro 5 sulfonic acid phenylamide.

acid

The aminobenzenes which can be used in the practice of our invention arediazotized and coupled with phenolic or enolic compounds which couple inortho position to the hydroxyl group. If the coupling in ortho positionis ensured the phenols may contain any number and any type ofsubstituents, such as halogen, alkyl or amino groups. If the phenolscontain amino groups, the hydrogen atoms of the amino groups may besubstituted by" one or two alkyl radicals or one acyl radical. Asexamples of such compounds there may be mentioned substituted phenols,such as para cresol, halogenated phenols, meta or para amino orN-alkylated amino phenols, and N-acetyl or N-benzoyl amino phenols.

to ahydroxyl group, for example, naphthols, oxyquinolines or quinolones,such as 2-oxynaphthalene, l-amino-' 7-hydroxynaphthalene, the aminogroup of which has been substituted by an acyl or carboalkoxy group,hydroxy 6 brornonaphthalene, 1 hydroxy 5,8 dichloro naphthalene, 1hydroxy 4 benzoyl naph thalene,1-methyl-2,4-dioxo-1,2,3,4-tetrahydroquinolone.

The azo dyestuffs obtained by the coupling reaction are converted to thecomplex cobalt containing dyestuffs by reacting them with cobaltcompounds according to the conditions described in the American patentspecification 2,230,686. According to this method the azo dyestuffs areheated in a liquid medium containing the cobalt compound and acid amidesor ammonium salts of carboxylic acids. Among suitable amides there arementioned, for example, formamide, acetamide, benzamide, malonic aciddiamide or urea. Suitable ammonium salts are, for example, ammoniumformate and acetate.

Instead of the compounds listed in the above-mentioned U. S. patentspecification ammonia or amines, such as methylamine, ethylamine,hexylamine, dodecylamine, di-

ethylamine, trimethylamine, and pyridine can also be used as solvents.The presence of water is harmless. In a convenient manner of working theazo component is mixed with the metal compound and the solvent, and themixture is heated to the required temperature. Another method of workingconsists in using the molten ammonium salts of aliphatic carb'oxylicacids as solvents or' converting the amides of aliphatic carboxylicacids into the respective ammonium carbonates by heating with aqueousmetal salt solutions and causing the complex metal dyestufi to be formedin the melt obtained after introducing the azo component. Other suitablesolvents are, for example, polyhydric alcohols, triethanolamine orketones.

The cobalt compounds may be for example the formate, acetate, sulfate,chloride or any other salt of bivalent and trivalent cobalt. Othersuitable cobalt compounds are complex compounds of the formula [Co(NH C1and [CoCl(NH C1 The cobalt salts or complex compounds need not bereadily soluble in the solvents used, since very small amounts ofdissolved cobalt compound will already be suificient to set the reactionto the complex metal dyestufi going and terminate it completely. As arule, for two molecules of the monoazo dyestuffs, about one molecule ofthe cobalt compound is used. During the reactionwith the azo dyestuffsbivalent cobalt is converted to trivalent cobalt. The reaction betweenthe azo dyestuffs and the cobalt compounds, which is usually called ametallization, is preferably carried out at a temperature between to C.Generally a reaction time between one and five hours is required. It isnot necessary to maintain a definite pH-value, if the metallization iscarried out in the manner above referred to.

The alkoxy groups adjacent to the azo groups are Other suitable couplingcompounds are those coupling in ortho position The new cobalt complexdyestufis obtained by the above reaction have in their anionic form thegeneral formula i \Z X are obtained.

For the reaction with the cobalt compounds, equimolecular mixtures oftwo diflerent azo dyestuffs may be used instead of only one azodyestuff, or equivalent pro- A portions of several azo dyestuffs may beused. In addition to the described azo dyestuffs in such mixtures, oneof the components may be another azo dyestuif, for example, an azodyestuff obtained by coupling a diazotized aminobenzene sulfonic acidamide with a pyrazolone derivative. The following general formulaincludes these unsymmetrical dyestuffs In this formula X, Y and Z havethe same meaning as defined for the l-alkoxy-Z-aminobenzene sulfonicacid amides employed as initial material; A stands for an aryl, aquinolyl or dihydro-Z-oxo-quinolyl radical which contains the linkage tothe azo group and the linkage to the oxygen atom connected with thecobalt atom on adjacent carbon atoms; B and C are organic radicals,preferably aromatic radicals or heterocyclic such as quinolyl ordihydro-Z-oxoquinolyl or pyrazole radicals containing the linkage to theazo group and the linkage to the oxygen atom connected with the cobaltatom on adjacent carbon atoms.

The new complex azo dyestuffs are very fast to light, perspiration andwashing, and give very even shades. In many cases, they have asurprisingly better light fastness than the chromium containing complexazo dyestuffs. For example the complex cobalt dyestufr from l.4di-

*1; methoxy-2-aminobenzene-S-sulfonamide and Z-hydroxynaphthalene (of.Example 11) has a light fastness of 7, whereas the corresponding complexchromium dyestutf has a light fastness of only 5 to 6. The new complexcobalt dyestuffs can be used by themselves or in mixtures with eachother or with other metal-containing or metal-free azo dystuffs. Theyare of particular interest for dyeing wool and polyamide textiles,fibers, fabrics or other polyamide articles. The term polyamide includesthe condensation products obtained from diamines and dicarboxylic acids,from aminocarboxylic acids, from lactames, or from mixtures of suchcompounds. The dyestuffs are applied from a neutral or slightly acidbath.

The following are representative examples of the invention, and it is tobe understood that the invention is not limited thereto nor to thespecific compounds, proportions or procedures therein, which are setforth only for purposes of illustration. The parts are by weight. Theraction of initial materials in Examples 4 to 17 is performed as inExamples 1 and 2.

Example 1 20 parts of the monoazo dyestufl obtained by couplingdiazotized 1 methoxy 2 amino-4-methyl-benzene-S- sulfonic acid amide tol-oxy-4-isobutyl benzene are heated with a solution of 11 parts ofcobalt acetate in 200 parts of acetamide for five hours at 130 C. Thereaction mixture is introduced then into 200 parts of water, and 200parts of sodium chloride are added to this mixture. The precipitateddyestufi is filtered, washed with Water and driedat C.

The dyestuif dyes wool in a slightly acid bath in a Bordeaux red shadehaving very good fastness properties.

Instead of cobalt acetate, other cobalt salts such as cobalt formate,chloride, sulfate and complex cobalt compounds, such as [Co(NH ]Cl and[CoCl(NH ]Cl are suitable, the particular kind of cobalt salt or complexcobalt compound used being selected with regard to their availability.

Example 2 8 parts of CoCl .6H O are dissolved in 200 parts of pyridine.Into this solution are introduced at a temperature of C. 21 parts of anazo dyestuff obtained by coupling diazotized1,4-dimethoxy-Z-amino-benzene- S-sulfonic acid amide tol-carbomethoxyamino-7-naph thol. The reaction mixture is refluxed forfour hours and poured into 200 parts of water. A blue dyestutf is (a) 9parts of the azo dyestuff obtained by coupling diazotizedl-methoxy-Z-amino 4 methylbenzene 5- sulfonic acid-methylamide tol-acetamino-7-oxynaphthalene; and

(b) 10 parts of the azo dyestuii obtained by coupling diazotizedl-methoxy-2 amino benzene 4 sulfonic acid-methylamide to1-phenyl-B-methyl-pyrazoloned.

The mixture is heated for five hours to 150" C. and poured into 200parts of water. The brown dyestufl obtained is filtered, washed withwater and dried.

Examples 4-17 In like manner, new complex cobalt dyestufis are producedaccording to the invention by reacting one of the described cobaltcompounds with the azo dyestuffs obtained by coupling the diazocompounds of the followmg amines wlth the 1nd1cated coupling compounds.

Shade of Example Amine Coupling Compound the Dyemg on Wool 41-methoxy-2-amino- 1-methyl-2,4-dioxo- Yellow- 4-methyl-benzene-1,2,3,4-tetrahydroish-red. fi-sulfonamide. quinoline.

5 do l-hydrox -2,4-dlehlo- Bordeaux robenzene. re

6 do 2-l11ydroxy-naphtha- Violet.

ene.

7 do 1-hydroxy-5,8-dichlo- Do.

ronaphthalene.

8 1-n1ethoxy-2-amlno-4- 1-aeetamino-7-hy- Reddishmethyl-benzene-S-drew-naphthalene. blue. sulfonic acid ethylamide.

9 l-methoxy-Z-amino il-hydroxy-i-methyl- Bordeauxchlorobenzene-fibenzene. re sulfonie acid-phenylamide.

10 1-methoxy-2-aminO-4- l-earbomethoxyaml- Blue. chlorobenzene-S-no-7-hydroxysulfonamide. naphthalene.

11 1,4-dlmethoxy-2aml- 2-hydroxy-naphtha- Blulshnobenzene-fi-sulfonlene.violet. amide.

12 do 2-hydroxy-6-bromo- Do.

naphthalene.

13 do l-hydroxy-5,8-dichlo- Reddlshro-naphthalene. blue.

14 1,4-dlethoxy-2-amin0- 1-acetamino-7-hy- Blue.

benzene-fi-sulfonic droxynaphthalene. aeld-methylamide.

15 1-methoxy-2-amino-4- l-hydroxyA-benzoyl- Violet.

methyl-benzene-5- naphthalene. sulfonamlde.

16 1,4-dlethoxy-2-amlno- 1-hydroxy-4-acetem1- Do.

benzene-5-sulfonie nobenzene. irzld-dlmethylam- 17 1,4-diethoxy-2-amino-1-hydroxy-3-diethyl- Do.

benzene-S-sulfonaminobenzene. amide.

The dyestufi of Example 11 above has in 1ts amomc form the formula NHaSOOCH:

The dyestufl of Example 12 above has in its anionic 60 form the formulaThe dyestuff of Example 14 above has in its anionic form the formula OCIHE O CzHs The invention is hereby claimed as follows: A complexcobalt-containing azo dyestuff having in its anionic form the formulaOCH: CHIOOC NH N=N- somnl NHCOOCH: eon.

References Cited in the file of this patent UNITED STATES PATENTS2,230,686 Holzach et al. Feb. 4, 1941 2,671,081 Bilings et al. Mar. 2,1954 2,673,199 Widmer et a1. Mar. 23, 1954 2,749,332 Buehler et al. June2, 1956 2,757,172 Schetty et al. July 31, 1956 FOREIGN PATENTS 1,061,365France Nov. 25, 1953

1. A COMPLEX COBALT-CONTAINING AZO DYESTUFF HAVING IN ITS ANIONIC FORMTHE FORMULA